JP2020508368A - Copolymer and organic solar cell containing the same - Google Patents

Abstract

The present specification describes a copolymer containing a repeating unit derived from a compound represented by Chemical Formula 1, a first conjugated monomer, and a second conjugated monomer different from the first conjugated monomer, and a copolymer containing the same. Provide organic solar cells.

Description

  This specification claims the benefit of the filing date of Korean Patent Application No. 10-2017-0085866, filed on July 6, 2017, with the Korean Patent Office, the entire contents of which are incorporated herein.

  The present specification relates to a copolymer and an organic solar cell including the same.

  An organic solar cell is a device that can directly convert solar energy into electric energy by applying a photovoltaic effect. Solar cells are classified into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is one in which crystalline silicon (Si), which is an inorganic semiconductor, is doped to form a pn junction. Electrons and holes generated by absorbing light diffuse to the pn junction, and are accelerated by the electric field to move to the electrodes. The power conversion efficiency in this process is defined by the ratio of the power supplied to the external circuit to the solar power input to the solar cell, and has been achieved up to about 24% when measured under currently standardized virtual solar irradiation conditions. However, conventional inorganic solar cells have already reached their limits in terms of economic efficiency and supply and demand in terms of materials, so organic semiconductor solar cells that are easy to process, inexpensive and have various functions are a long-term alternative energy source. Attention has been paid.

  It is important to increase the efficiency of a solar cell so that it can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is important to generate as many excitons as possible inside the semiconductor, but it is also important to extract the generated charges to the outside without loss. One of the causes of the loss of charge is that generated electrons and holes disappear by recombination. Although various methods have been proposed for transferring the generated electrons and holes to the electrode without loss, almost additional steps are required, which may increase manufacturing costs.

  It is an object of the present specification to provide a copolymer and an organic solar cell including the same.

The present specification relates to a repeating unit derived from a compound represented by the following chemical formula 1:
A copolymer comprising a first conjugated monomer; and a second conjugated monomer different from the first conjugated monomer is provided.

In the above chemical formula 1,
m1 and m2 are the same or different and are each independently an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other;
q1 and q2 are the same or different and are each independently an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other;
A1 and A1 ′ are the same or different and are each independently a halogen group; a substituted or unsubstituted boron group; or —SnR _a R _b R _c ;
X1, X2 and Z1 to Z5 are the same or different from each other, and each independently is S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR ′;
R _a , R _b , R _c , R, R ′, R 1 to R 4 and R 11 to R 18 are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; Group; ester group; imide group; amide group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group; A substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted ant A substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.

Another embodiment of the present specification provides a first compound represented by the following Formula 1:
A method for producing a copolymer, comprising: reacting a second compound represented by the following Chemical Formula 2; and a third compound represented by the following Chemical Formula 3:

In the chemical formulas 1 to 3,
m1 and m2 are the same or different and are each independently an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other;
q1 and q2 are the same or different and are each independently an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other;
A1, A1 ′, A2, A2 ′, A3 and A3 ′ are the same or different and are each independently a halogen group; a substituted or unsubstituted boron group; or —SnR _a R _b R _c ,
E1 is a first conjugated monomer,
E2 is a second conjugate monomer different from the first conjugate monomer,
X1, X2 and Z1 to Z5 are the same or different from each other, and each independently is S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR ′;
R _a , R _b , R _c , R ₁ to R 4 and R 11 to R 18 are the same or different and are each independently hydrogen, deuterium, halogen, nitrile, nitro, hydroxy, carbonyl, ester; An imide group; an amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; Boron group; substituted or unsubstituted amine group; substituted or unsubstituted arylphosph Inmoto; or substituted or unsubstituted heterocyclic group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group.

Another embodiment herein comprises a first electrode,
A second electrode provided to face the first electrode;
And one or more organic layers including a photoactive layer, provided between the first electrode and the second electrode;
One or more of the organic material layers provide an organic solar cell including the copolymer.

  The copolymer according to an embodiment of the present specification exhibits planarity and has excellent aggregation characteristics and crystallinity.

  The copolymer according to an embodiment of the present specification may have an effect of reducing a band gap and / or increasing a light absorption amount. Accordingly, when applied to an organic solar cell, a high current value (Isc) is exhibited, so that excellent efficiency can be exhibited.

  The copolymer according to one embodiment of the present specification has appropriate solubility at the same time as achieving high efficiency, and has an economical advantage in terms of time and / or cost when manufacturing a device.

  The copolymer according to one embodiment of the present specification can be used alone or in a mixture with other substances in an organic solar cell.

1 is a diagram illustrating an organic solar cell according to an embodiment of the present specification. It is a figure which shows the NMR spectrum of compound 1-d. It is a figure which shows the MS spectrum of compound 1-d. It is a figure which shows the MS spectrum of compound 1-e. It is a figure which shows the MS spectrum of compound 1-f. It is a figure which shows the NMR spectrum of compound 1-f. It is a figure which shows the MS spectrum of compound 1-g.

  Hereinafter, the present specification will be described in detail.

  One embodiment of the present specification relates to a compound comprising a repeating unit derived from the compound represented by Chemical Formula 1, a first conjugated monomer, and a second conjugated monomer different from the first conjugated monomer. Provide a polymer.

  The repeating unit derived from the compound represented by Formula 1 includes a thiophene having an electron donor property and a benzothiadiazole structure having an electron acceptor property. Therefore, the intramolecular interaction between the thiophene and the benzothiadiazole improves the planarity and improves the crystallinity due to the intramolecular interaction.

  Further, the repeating unit derived from the compound represented by Formula 1 has excellent crystallinity by having a regioregularity in which R1 and R4 are substituted at certain positions.

  As used herein, “regioregularity” means that a substituent is provided in a certain direction in a structure in a polymer. For example, in Formula 1, R1 and R4 are substituted at a position relatively far from the heterocyclic group having Z3.

  In the present specification, the term “origin” means that a bond between at least two adjacent elements in a compound is cut or a new bond is generated as hydrogen or a substituent moves away, Can be a unit that forms one or more of the main chain and side chain of the copolymer. The unit can be included in the main chain of the copolymer to constitute the copolymer.

  In the present specification, a “repeating unit” is a structure in which a unit derived from a monomer is repeatedly contained in a copolymer, and one kind of a plurality of monomers is bonded into the copolymer by polymerization. Means the structure.

  In one embodiment of the present specification, “the repeating unit derived from the compound represented by Chemical Formula 1” may include the following structure in the main chain.

  In the above structure, Z1 to Z5, X1, X2, R1 to R4, R11 to R18, m1, m2, q1 and q2 are the same as defined in Chemical Formula 1.

  In this specification, when a portion is referred to as "including" a component, it means that, unless stated otherwise, the component can not only exclude the other component but also include another component. I do.

  As used herein, when an element is referred to as being "on" another element, this can occur not only when one element is in contact with another element, but also when another element is located between the two elements. This also includes the case where the member exists.

  In this specification, “combination” means connecting a plurality of one structure or connecting different types of structures.

  In the present specification, examples of the substituent are described below, but are not limited thereto.

は、他の置換基、単量体、または結合部に結合する部位を意味する。 In this specification,

Means a site bonded to another substituent, a monomer, or a bonding portion.

  In this specification, a monomer can mean a repeating unit contained in a polymer.

  In the present specification, examples of the substituent are described below, but are not limited thereto.

  The term `` substituted '' means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position of substitution is the position at which the hydrogen atom is substituted, that is, the substituent is substitutable. The position is not particularly limited, and if two or more substituents are present, the two or more substituents may be the same or different from each other.

  As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen; nitrile; nitro; imide; amide; carbonyl; ester; hydroxy; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkylsulfoxy group; Arylsulfoxy group; Alkenyl group; Silyl group; Siloxane group; Boron group; Amine group; Arylphosphine group; Phosphine oxide group; Or substituted with one or more substituents selected from the group consisting of heterocyclic groups, or two or more substituents among the substituents exemplified above are substituted with a linked substituent. Or does not have any substituents. For example, the “substituent in which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are linked.

  As used herein, a halogen group may be fluorine, chlorine, bromine, or iodine.

  In this specification, the number of carbon atoms of the imide group is not particularly limited, but preferably has 1 to 30 carbon atoms.

  In the present specification, in the amide group, the nitrogen of the amide group may be substituted with hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. .

  In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but preferably has 1 to 30 carbon atoms.

  In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

  In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, iso Hexyl, 4-methylhexyl, 5-methylhexyl there are like, but is not limited thereto.

  In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, Examples include, but are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. Absent.

  In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but preferably has 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n- It may be hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, but is not limited thereto. Not something.

In this specification, the amine group, -NH _2; consisting of N- alkylheteroaryl amine groups and heteroaryl amine groups; alkylamine group; N- arylalkyl amine; arylamine group; N- aryl heteroaryl amine It may be selected from a group, and the number of carbon atoms is not particularly limited. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, Examples include, but are not limited to, N-phenylnaphthylamine groups, ditolylamine groups, N-phenyltolylamine groups, triphenylamine groups, and the like.

  In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

  In the present specification, the N-arylheteroarylamine group means an amine group in which N of the amine group is substituted with an aryl group and a heteroaryl group.

  In the present specification, an N-alkylheteroarylamine group means an amine group in which N of an amine group is substituted with an alkyl group and a heteroaryl group.

  In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkylsulfoxy group, and the N-alkylheteroarylamine group are as exemplified above for the alkyl group. Specifically, examples of the alkylthioxy group include a methylthioxy group, an ethylthioxy group, a tert-butylthioxy group, a hexylthioxy group, and an octylthioxy group.Examples of the alkylsulfoxy group include mesyl, ethylsulfoxy, Examples include, but are not limited to, propylsulfoxy and butylsulfoxy groups.

  In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3- Butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthyl-1-yl) vinyl-1- Yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.

  In the present specification, a silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group. And the like, but are not limited to these.

In the present specification, boron group _may be a -BR _{100 R 200,} wherein _{R 100} and _{R 200} are identical or different, each independently, hydrogen, deuterium, halogen, nitrile group, a substituted or unsubstituted Substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; substituted or unsubstituted having 6 to 30 carbon atoms It may be selected from the group consisting of a monocyclic or polycyclic aryl group; and a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

  In the present specification, the phosphine oxide group specifically includes, but is not limited to, a diphenylphosphine oxide group and a dinaphthylphosphine oxide.

  As used herein, an aryl group may be monocyclic or polycyclic.

  When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably has 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, and the like.

  When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but preferably has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, or the like, but is not limited thereto.

  In the present specification, the fluorenyl group may be substituted, or adjacent substituents may be bonded to each other to form a ring.

などになってもよい。ただし、これらに限定されるものではない。 When the fluorenyl group is substituted,

And so on. However, it is not limited to these.

  In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylamine group, and the arylphosphine group is exemplified by the aforementioned aryl group. It is as follows. Specifically, examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, and a p-tert-butylphenoxy group. , 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy Group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like. As the arylthioxy group, A phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group and the like; The benzene sulfoxide group, p- there and toluene sulfoxide group, but is not limited thereto.

  In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, and a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group simultaneously. For example, the aryl group in the arylamine group may be selected from the above-described examples of the aryl group.

  In the present specification, the heterocyclic group includes one or more non-carbon atoms and hetero atoms. Specifically, the hetero atoms are selected from the group consisting of O, N, Se, S, and the like. One or more atoms. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, triazolyl, acridyl, pyridazinyl, Pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, Benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazoli Group, thiadiazolyl group, phenothiazinyl group, and the like dibenzofuranyl group, but is not limited thereto.

  In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, and a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group containing two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group simultaneously. For example, the heteroaryl group in the heteroarylamine group may be selected from the above-mentioned examples of the heterocyclic group.

  In the present specification, examples of the N-arylheteroarylamine group and the heteroaryl group in the N-alkylheteroarylamine group are the same as those of the heterocyclic group described above.

  In one embodiment of the present specification, the copolymer includes a unit represented by the following Chemical Formula 1-1.

In the chemical formula 1-1,
m1, m2, m1 ′ and m2 ′ are the same or different from each other and are each independently an integer of 0 to 5,
When m1, m2, m1 ′ and m2 ′ are each 2 or more, the structures in parentheses are the same or different from each other;
q1, q2, q1 ′ and q2 ′ are the same or different from each other and are each independently an integer of 1 to 5,
When q1, q2, q1 ′ and q2 ′ are each 2 or more, the structures in parentheses are the same or different from each other;
X1, X2, X1 ′, X2 ′, Z1 to Z5 and Z1 ′ to Z5 ′ are the same or different from each other, and each independently represents S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR. '
E1 is a first conjugated monomer,
E2 is a second conjugated monomer,
R, R ', R1 to R4, R1' to R4 ', R11 to R18 and R11' to R18 'are the same or different and are each independently hydrogen; deuterium; halogen; nitrile; nitro; An amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted group. A substituted or unsubstituted amine group; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group. ,
f is a mole fraction and is a real number satisfying 0 <f <1;
g is a molar fraction and is a real number satisfying 0 <g <1;
f + g = 1,
n is the number of repeating units, and is an integer of 1 to 10,000.

  As used herein, the term "conjugated monomer" means one in which two or more multiple bonds are present with one single bond interposed therebetween in the structure of the compound and exhibit an interaction. At this time, the conjugated monomer means both the first conjugated monomer and the second conjugated monomer.

  In this specification, a conjugated monomer can mean a repeating unit derived from a conjugated monomer contained in a polymer.

  In one embodiment of the present specification, the first conjugate monomer and the second conjugate monomer are each independently a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted And a combination of one or more of the divalent heterocyclic groups.

  In the present specification, the description regarding the alkenyl group described above is applicable except that the alkenylene group is a divalent group.

  In the present specification, the above description regarding the aryl group can be applied, except that the arylene group is a divalent group.

  In the present specification, the description regarding the heterocyclic group described above is applicable except that the divalent heterocyclic group is a divalent group.

  According to one embodiment of the present specification, the conjugated monomer includes an electron donor structure or an electron acceptor structure.

  In one embodiment of the present specification, the first conjugate monomer and the second conjugate monomer each independently include any one or a combination of two or more of the following structures.

In the above structure,
a, a ', b and b' are each an integer of 1 to 5,
When a, a ', b and b' are each 2 or more, the substituents in parentheses are the same or different from each other;
X11~X30 and X33~X40, equal to or different from each other, each _{independently, S, O, Se, Te} , NR d, CR d R e, a SiR _d R e, PR _d or _GeR d _{R e,,}
X31 and X32 are the same or different from each other, and each is independently C, Si, or Ge;
R101~R124, _{R d} and _{R e,} equal to or different from each other, each independently, hydrogen, deuterium, a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; amide group; substituted Or a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, or a substituted or unsubstituted arylthioxy A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; An amine group; a substituted or unsubstituted arylphosphine group; Ku is unsubstituted phosphine oxide group; or a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted aryl group.

  In one embodiment of the present specification, the first conjugate monomer and the second conjugate monomer each have any one of the following structures.

In the above structure,
X11~X14, X19, X20, X33~X40, X11 ' and X11'', equal to or different from each other, each _{independently, S, O, Se, Te} , NR d, CR d R e, SiR d R e, is a PR _d or _GeR d _{R e,,}
R101~R110, R117~R124, R101 ', R101 '',R102', R102 '', R d and _{R e,} equal to or different from each other, each independently, hydrogen, deuterium, a halogen group; a nitrile group; a nitro A hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkylthioxy group; a substituted or unsubstituted arylthioxy group; a substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; Unsubstituted silyl group; substituted or unsubstituted boron group; substituted or unsubstituted Conversion of the amine groups; or substituted or unsubstituted heterocyclic group; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group.

In one embodiment of the present specification, the X11~X14, X19, X20, X33~X40, X11 ' and X11'', equal to or different from each other, each independently, S or _{CR d R e, R} d And _Re are the same as described above.

  In one embodiment of the present specification, X11 to X14, X19, X20, X33 to X36, X39, X40, X11 'and X11 "are each S.

In one embodiment of the present specification, the X37 and X38 are _CR d _{R e, R d} and _{R e} is a substituted or unsubstituted aryl group.

  In one embodiment of the present specification, R101 to R110, R117 to R124, R101 ′, R101 ″, R102 ′, and R102 ″ are the same or different from each other, and each independently represents hydrogen; a halogen group; A substituted or unsubstituted alkoxy group; or a substituted or unsubstituted heterocyclic group.

  In one embodiment of the present specification, R101 and R102 are each hydrogen.

  In one embodiment of the present specification, R 101, R 101 ′, R 101 ″, R 102, R 102 ′, and R 102 ″ are the same or different and are each independently hydrogen; a substituted or unsubstituted alkyl group; Alternatively, it is an unsubstituted alkoxy group.

  In one embodiment of the present specification, R 101, R 101 ′, R 101 ″, R 102, R 102 ′, and R 102 ″ are the same or different and are each independently hydrogen; an alkyl group having 1 to 15 carbon atoms; It is a substituted or unsubstituted alkoxy group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R103 to R108 are the same or different and are each independently hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R103 and R108 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

  In one embodiment of the present specification, R104 and R107 are hydrogen.

  In one embodiment of the present specification, R105 and R106 are the same or different from each other, and are each independently a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R105 and R106 are the same as or different from each other, and are each independently a substituted or unsubstituted alkoxy group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R109 and R110 are the same or different and are each independently a substituted or unsubstituted heterocyclic group.

  In one embodiment of the present specification, R109 and R110 are the same or different from each other, and are each independently a heterocyclic group substituted with an alkyl group.

  In one embodiment of the present specification, R109 and R110 are the same or different from each other, and are each independently a thiophene group substituted with an alkyl group.

  In one embodiment of the present specification, R121 and R122 are the same or different from each other, and are each independently a halogen group.

  In one embodiment of the present specification, R121 and R122 are fluorine.

  In one embodiment of the present specification, R117 to R120 are the same or different and are each independently hydrogen; or a substituted or unsubstituted alkyl group.

  In one embodiment of the present specification, R117 and R120 are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group.

  In one embodiment of the present specification, R117 and R120 are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R117 and R120 are the same or different from each other, and are each independently a branched alkyl group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R118 and R119 are hydrogen.

  In one embodiment of the present specification, R123 and R124 are hydrogen.

  In one embodiment of the present specification, the first conjugate monomer and the second conjugate monomer each have any one of the following structures. That is, E1 and E2 each have any one of the following structures.

  In one embodiment of the present specification, the copolymer includes a unit represented by the following Chemical Formula 1-2.

In the above chemical formula 1-2,
f, g, n, m1, m2, m1 ′, m2 ′, q1, q2, q1 ′, q2 ′, X1, X2, X1 ′, X2 ′, Z1 to Z5, Z1 ′ to Z5 ′, E1, E2, R1, R4, R1 ′, R4 ′, R11 to R18 and R11 ′ to R18 ′ are the same as defined in Chemical formula 1-1,
R51, R51 ′, R52 and R52 ′ are the same or different and are each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

  In one embodiment of the present specification, R51, R51 ', R52, and R52' are the same or different from each other, and are each independently a substituted or unsubstituted alkyl group.

  In one embodiment of the present specification, R51, R51 ', R52, and R52' are the same or different from each other, and are each independently an alkyl group having 1 to 30 carbon atoms.

  In one embodiment of the present specification, R51, R51 ', R52 and R52' are the same or different from each other, and are each independently an alkyl group having 1 to 20 carbon atoms.

  In one embodiment of the present specification, R51, R51 ', R52 and R52' are the same as each other and each independently represents an alkyl group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R1 to R4 and R11 to R18 are the same or different from each other and are each independently hydrogen; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; Or an unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.

  In one embodiment of the present specification, R1 to R4 and R11 to R18 are the same or different and are each independently a hydrogen; a halogen group; or a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R1 and R4 are the same or different from each other, and are each independently a halogen group.

  In one embodiment of the present specification, R1 and R4 are fluorine.

  In one embodiment of the present specification, R2 and R3 are each a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R2 and R3 are each a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

  In one embodiment of the present specification, R2 and R3 are each a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

  In one embodiment of the present specification, R2 and R3 are each an alkoxy group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R11 to R18 are hydrogen.

  In one embodiment of the present specification, Z1 to Z5 and Z1 'to Z5' are S.

  In one embodiment of the present specification, X1 and X2 are S.

  In one embodiment of the present specification, R1 ′ to R4 ′ and R11 ′ to R18 ′ are the same or different and are each independently hydrogen; a halogen group; a substituted or unsubstituted alkyl group; An alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.

  In one embodiment of the present specification, R1 'to R4' and R11 'to R18' are the same or different and are each independently a hydrogen; a halogen group; or a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R1 'and R4' are the same or different from each other, and are each independently a halogen group.

  In one embodiment of the present specification, R1 'and R4' are fluorine.

  In one embodiment of the present specification, R2 'and R3' are a substituted or unsubstituted alkoxy group.

  In one embodiment of the present specification, R2 'and R3' are each a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

  In one embodiment of the present specification, R2 'and R3' are each a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

  In one embodiment of the present specification, R2 'and R3' are each an alkoxy group having 1 to 15 carbon atoms.

  In one embodiment of the present specification, R11 'to R18' are hydrogen.

  In one embodiment of the present specification, m1, m2, m1 ', m2', q1, q2, q1 'and q2' are each 1.

  In one embodiment of the present specification, the copolymer includes any one of the following structures.

In the above structure,
f is a mole fraction and is a real number satisfying 0 <f <1;
g is a molar fraction and is a real number satisfying 0 <g <1;
f + g = 1,
n is the number of repeating units, and is an integer of 1 to 10,000.

  In one embodiment of the present specification, f and g are the same or different from each other, each is a real number of 0.3 to 0.7, and f + g = 1.

  In one embodiment of the present specification, f is 0.3 and g is 0.7.

  In one embodiment of the present specification, f is 0.7 and g is 0.3.

  In one embodiment of the present specification, the terminal group of the copolymer is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Specifically, in one embodiment of the present specification, the terminal group of the copolymer is a thiophene group or a substituted or unsubstituted phenyl group.

  In one embodiment of the present specification, the copolymer has a number average molecular weight of 2,000 g / mol to 30,000,000 g / mol. Preferably, the copolymer has a number average molecular weight of 5,000 g / mol to 10,000,000 g / mol. More preferably, the copolymer has a number average molecular weight of 10,000 g / mol to 5,000,000 g / mol.

  In one embodiment of the present specification, the copolymer may have a molecular weight distribution (PDI) of 1 to 100. Preferably, the copolymer has a molecular weight distribution of 1-3.

One embodiment of the present specification provides a first compound represented by the following Chemical Formula 1:
A method for producing a copolymer, comprising: reacting a second compound represented by the following Chemical Formula 2; and a third compound represented by the following Chemical Formula 3:

In the chemical formulas 1 to 3,
m1 and m2 are the same or different and are each independently an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other;
q1 and q2 are the same or different and are each independently an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other;
A1, A1 ′, A2, A2 ′, A3 and A3 ′ are the same or different and are each independently a halogen group; a substituted or unsubstituted boron group; or —SnR _a R _b R _c ,
E1 is a first conjugated monomer,
E2 is a second conjugate monomer different from the first conjugate monomer,
X1, X2 and Z1 to Z5 are the same or different from each other, and each independently is S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR ′;
R _a , R _b , R _c , R, R ′, R 1 to R 4 and R 11 to R 18 are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; Group; ester group; imide group; amide group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group; A substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted ant A substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, A1, A1 ′, A2, A2 ′, A3 and A3 ′ are the same or different from each other, and each independently represents _a halogen group; or —SnR _a R _b R _c , _a , R _b , and R _c are as described above.

In one embodiment of the present specification, A1, A1 ′, A2, A2 ′, A3 and A3 ′ are the same or different from each other, and are each independently bromine or —SnR _a R _b R _c , and R _a , R _b , and R _c are methyl groups.

  In one embodiment of the present specification, Chemical Formula 1 of the method for producing the copolymer is the same as Chemical Formula 1 of the copolymer described above.

  In one embodiment of the present specification, E1 of Formula 2 and E2 of Formula 3 are the same as defined for the copolymer. For example, E1 and E2 are different from each other and each has one of the following structures.

  In one embodiment of the present specification, the method for producing a copolymer includes a step of dissolving a first compound; a second compound; and a third compound in a solvent.

  In one embodiment of the present specification, the solvent may be chlorobenzene, dichlorobenzene, or trichlorobenzene.

  In one embodiment of the present specification, the content of the second compound in the solution is 0.3 mol to 0.7 mol based on 1 mol of the first compound.

  In one embodiment of the present specification, the content of the third compound in the solution is 0.3 mol to 0.7 mol based on 1 mol of the first compound.

  In one embodiment of the present specification, the solution means a solution in which the first compound, the second compound, and the third compound are dissolved in the solvent.

  In one embodiment of the present specification, the method for producing a copolymer includes a step of dissolving a first compound, a second compound, and a third compound in the first solvent and then refluxing the mixture at 90 ° C to 150 ° C. including.

One embodiment herein includes a first electrode;
A second electrode provided to face the first electrode;
Provided between the first electrode and the second electrode, including one or more organic layers including a photoactive layer;
One or more of the organic material layers provide an organic solar cell including the copolymer.

  FIG. 1 illustrates an organic solar cell according to one embodiment of the present specification, including a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105. It is.

  In one embodiment of the present specification, the organic solar cell may further include an additional organic material layer. The organic solar cell can reduce the number of organic material layers by using organic materials having various functions at the same time.

  In one embodiment of the present specification, the organic solar cell includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transport layer, and / or an electron transport layer.

  In one embodiment of the present specification, the photoactive layer includes the copolymer.

  In one embodiment of the present specification, the organic material layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously performs hole transport and hole injection, wherein the hole transport layer, the hole injection layer, Alternatively, a layer that simultaneously performs hole transport and hole injection contains the copolymer.

  In another embodiment, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that performs electron injection and electron transport simultaneously, and the electron injection layer, the electron transport layer, or the electron injection and electron transport simultaneously. The layer to be performed contains the copolymer.

  In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode. In another embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

  In one embodiment herein, the organic solar cell may be arranged in the order of a cathode, a photoactive layer, and an anode, or may be arranged in the order of an anode, a photoactive layer, and a cathode, but is not limited thereto. Not done.

  In another embodiment, the organic solar cell may be arranged in the order of an anode, a hole transport layer, a photoactive layer, an electron transport layer, and a cathode, wherein the cathode, the electron transport layer, the photoactive layer, the hole The transport layer and the anode may be arranged in this order, but are not limited thereto.

  In one embodiment of the present specification, the photoactive layer includes an electron donor and an acceptor, and the electron donor includes the copolymer.

In one embodiment of the present specification, the electron acceptor substance may be selected from the group consisting of fullerene, fullerene derivative, bathocuproine, semiconductive element, semiconductive compound, and a combination thereof. Specifically, the electron acceptor _{material, PC 60 BM (phenyl C 60} -butyric acid methyl ester), PC 61 BM (phenyl C 61 -butyric acid methyl ester), or _PC 71 BM _(phenyl C 71 _-butyric acid methyl ester).

  In one embodiment of the present specification, the electron donor and the electron acceptor constitute a bulk heterojunction (BHJ). The electron donor material and the electron acceptor material are mixed in a ratio (w / w) of 1:10 to 10: 1. Specifically, the electron donor material and the electron acceptor material are mixed in a ratio (w / w) of 1: 1 to 1:10, and more specifically, the electron donor material and the electron acceptor material are , 1: 1 to 1: 5 (w / w). If necessary, the electron donor material and the electron acceptor material may be mixed in a ratio (w / w) of 1: 1 to 1: 3.

  In one embodiment of the present specification, the photoactive layer has a two-layer thin-film structure including an n-type organic material layer and a p-type organic material layer, and the p-type organic material layer includes the copolymer.

  In the present specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is generally used for an organic solar cell. There is no limitation as long as the substrate can be used. Specific examples include, but are not limited to, glass, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PP (polypropylene), PI (polyimide), and TAC (triacetyl cellulose).

The first electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO : A combination of metal and oxide such as Al or SnO ₂ : Sb; poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline However, the conductive polymer is not limited thereto.

  The method of forming the first electrode is not particularly limited, but is applied to one surface of the substrate using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade, or gravure printing. Alternatively, it is formed by coating in a film form.

  When the first electrode is formed on a substrate, the first electrode may be subjected to washing, removing water, and modifying hydrophilicity.

  For example, after the patterned ITO substrate is sequentially washed with a cleaning agent, acetone, and isopropyl alcohol (IPA), in order to remove moisture, a heating plate is used at 100 ° C. to 150 ° C. for 1 minute to 30 minutes, preferably 120 minutes. After drying at 10 ° C. for 10 minutes and the substrate being completely washed, the surface of the substrate is modified to be hydrophilic.

  By such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, at the time of the modification, the formation of the polymer thin film on the first electrode becomes easy, and the quality of the thin film can be improved.

  The pretreatment techniques for the first electrode include a) a surface oxidation method using a parallel plate type discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) plasma. Oxidation using the oxygen radicals generated by the method.

  One of the above methods can be selected according to the state of the first electrode or the substrate. However, regardless of which method is used, it is commonly preferable to prevent the desorption of oxygen from the surface of the first electrode or the substrate and to suppress the remaining of moisture and organic substances to the maximum. At this time, the substantial effect of the pretreatment can be maximized.

  As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, after the ultrasonic cleaning, the patterned ITO substrate is baked with a heating plate (hot plate) and dried well, then put into a chamber, and a UV lamp is actuated to cause oxygen gas to emit UV light. The ITO substrate patterned by ozone generated by reacting with the substrate can be washed.

  However, the method for modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it oxidizes the substrate.

The second electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ , Al: BaF ₂ : Ba may be a material having a multilayer structure, but is not limited thereto.

The second electrode is formed by being deposited in a thermal evaporator having a degree of vacuum of 5 × 10 ⁻⁷ torr or less, but is not limited thereto.

  The material of the hole transport layer and / or the electron transport layer plays a role of efficiently transmitting electrons and holes separated by the photoactive layer to the electrode, and does not particularly limit the material.

The hole transport layer material may be PEDOT: PSS (Poly (3,4-ethylenedioxythiophene) doped with poly (styrenesulfonic acid)), molybdenum oxide (MoO _x ), vanadium oxide (V ₂ O ₅ ); nickel oxide. (NiO); and tungsten oxide (WO _x ), but are not limited thereto.

The ETL material may be made to the electronic extract metal oxides (electron-extracting metal oxides), specifically, a metal complex of 8-hydroxyquinoline; metal complex containing Liq; complexes including Alq ₃ LiF; Ca; titanium oxide (TiO _x ); zinc oxide (ZnO); and cesium carbonate (Cs ₂ CO ₃ ), but are not limited thereto.

  The photoactive layer is formed by dissolving a photoactive substance such as an electron donor and / or an electron acceptor in an organic solvent, and then spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, or the like. However, the present invention is not limited to only these methods.

  Production Example 1. Preparation of Compound 1-g

  (1) Production of compound 1-b

In 150 mL of toluene (toluenen), compound 1-a (10 g, 32.1 mmol) and 2- (trimethylstannyl) thiophene (2- (trimethylstannyl) thiophene) (8.15 g, 33.0 mmol) and tetrakis (triphenylphosphine) ) A palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.74 g, 0.64 mmol) was added and reacted at 110 ° C for 24 hours. After the reaction, the mixture was extracted with dichloromethane, the residue was removed with magnesium sulfate (MgSO ₄ ), and then the solvent was removed under reduced pressure. The residual product was passed through a silica column (silica column, eluent: hexane) to give 9.51 g of compound 1-b. (Yield: 94%)

  (2) Production of compound 1-d

In 120 mL toluene (toluene), compound 1-b (9 g, 28.56 mmol) and 2-trimethylstannyl-5-trimethylsilane-thiophene (2-trimethylstannyl-5-trimethylsilane-thiophene) (9.41 g, 29.5 mmol). ) And tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.65 g, 0.56 mmol) were added and reacted at 110 ° C. for 24 hours. After the reaction, the mixture was extracted with dichloromethane, the residue was removed with magnesium sulfate (MgSO ₄ ), and then the solvent was removed under reduced pressure. The residual product was passed through a silica column (silica column, eluent: hexane) to obtain 10.0 g of a compound 1-c. (Yield: 90%)

After dissolving compound 1-c (9.76 g, 25.00 mmol) in 200 mL tetrahydrofuran (THF), 2M lithium diisopropylamide (LDA) (15.0 mL, 30.00 mmol) is gradually added at −78 ° C. And stirred for 2 hours. Same temperature trimethyltin chloride _{(trimethyltinchloride, Me 3 SnCl) (} 33mL, 33mmol) put, after slowly raised to ambient temperature and react for 3 hours at room temperature. After the reaction, the mixture was extracted with dichloromethane, the residue was removed with magnesium sulfate (MgSO ₄ ), the solvent was removed under reduced pressure, and the compound 1-d was recrystallized from dichloromethane and methanol to give 12-d. 0.2 g was obtained. (88% yield)

  FIG. 2 is a diagram showing an NMR spectrum of the compound 1-d.

  FIG. 3 is a diagram showing an MS spectrum of the compound 1-d.

  (3) Production of compound 1-e

Compound A (2.75 g, 4.5 mmol) and compound 1-d (5.53 g, 10 mmol) are dissolved in 75 mL of toluene (toluenen) and 25 mL of dimethylformamide (DMF), and tetrakis (triphenylphosphine) palladium ( 0) A catalyst (Pd (PPh ₃ ) ₄ ) (0.2427 g, 0.21 mmol) was added, and the mixture was gradually heated and reacted at 90 ° C., 100 ° C., and 110 ° C. for 48 hours. The residue formed on cooling was precipitated with methanol, filtered and washed with water. Thereafter, the solvent is evaporated in a drying process, and the remaining product is purified by flash chromatography using methylene chloride and chloroform, and then recrystallized using methylene chloride and methanol. A blue solid was obtained. Thereafter, the solid was washed with methanol and dried under vacuum for 24 hours to obtain 4.71 g of compound 1-e. (Yield: 85%)

  FIG. 4 is a diagram showing an MS spectrum of the compound 1-e.

  (4) Production of compound 1-f

The compound 1-e (4.5 g, 3.66 mmol) is dissolved in 300 mL of tetrahydrofuran (THF) under a nitrogen atmosphere at normal temperature, and a tetrahydrofuran solution (1. Tetrabutylammonium fluoride, TBAF) in which tetrabutylammonium fluoride (TBAF) is dissolved. 0M, 10 mL, containing 10mmol, 5% _{H 2} O) was added dropwise to the resulting product was refluxed for two hours (reflux). Thereafter, 50 mL of ether (ether) and an aqueous solution of sodium hydrogen carbonate (NaHCO ₃ ) were added, and the mixture was stirred for 10 minutes. Thereafter, the resultant was washed with an aqueous solution of sodium chloride (NaCl), and the solvent was evaporated under a vacuum condition. The residual product was purified by flash chromatography using chloroform and then recrystallized using chloroform to obtain a dark purple solid. Thereafter, the solid was washed with water, methanol, hexane, ethyl acetate, and acetone, and dried under vacuum for 24 hours to obtain 3.15 g of compound 1-f. (Yield: 79%)

  FIG. 5 is a diagram showing an MS spectrum of compound 1-f.

  FIG. 6 is a diagram showing an NMR spectrum of the compound 1-f.

  (5) Production of compound 1-g

Compound 1-f (2.95 g, 2.72 mmol) and N-bromosuccinimide (NBS) (0.99 g, 5.58 mmol) were placed in 300 mL of chloroform (CHCl ₃ ) at 0 ° C. For 24 hours. Thereafter, the solvent was evaporated and the residue was purified by flash chromatography (flash chromatography, eluent (hexane to hexane: methylene chloride)) using the residue to obtain 2.1 g of compound 1-g. (Yield: 62%)

  FIG. 7 is a diagram showing an MS spectrum of compound 1-g.

  Production Example 2-1. Production of copolymer 1

In a 100 mL flask under a nitrogen (N ₂ ) atmosphere, 10 mL of chlorobenzene (CB), compound 1-g (0.6217 g, 0.5 mmol), compound A (0.2724 g, 0.35 mmol), and compound B (0.061 g, 0.15 mmol) was added, and nitrogen bubbling was performed for 30 minutes. Thereafter, a tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.11, 0.01 mmol) was added, and the mixture was stirred at 110 ° C. for 72 hours. After adding 0.5 mL of Br-benzotrifluoride, the mixture was stirred for 24 hours and cooled to room temperature. Thereafter, the product was poured into chloroform, passed through a short column with short silica, poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)), and the precipitate was filtered. Thereafter, the product was subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride, and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected, purified, and dried under vacuum to obtain 0.52 g of Copolymer 1. At this time, the number average molecular weight was measured to confirm that Copolymer 1 was produced. (Number average molecular weight: 29,000 g / mol, PDI: 1.34, yield: 73%)

Production Examples 2-2 to 2-36
The compound was prepared in the same manner as in Preparation Example 2-1 except that Compound A and Compound B in Preparation Example 2-1 were changed as shown in the following table.

  In Table 1, A to I are the following compounds, respectively.

Embodiment 1 FIG.
Using the copolymer 1 prepared in Preparation Example 1 as a donor and PCBM as an acceptor, the copolymer 1 was dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had a structure of ITO / ZnO / photoactive layer / MoO ₃ / Ag. The glass substrate coated with ITO was subjected to ultrasonic cleaning using distilled water, acetone, and 2-propanol, and the surface of the ITO was treated with ozone for 10 minutes. Then, the ZnO precursor solution was spin-coated, and the coating was performed at 120 ° C. for 10 minutes. Heat treated. Thereafter, the composite solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated to form a photoactive layer. Thereafter, MoO ₃ was deposited on the photoactive layer at a rate of 0.4 ° / s to a thickness of 5 nm to 20 nm using a thermal evaporator to manufacture a hole transport layer. Thereafter, Ag was deposited on the hole transport layer to a thickness of 10 nm in the thermal evaporator at a rate of 1Å / s to manufacture an organic solar cell.

Embodiment 2. FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-3 was used instead of the copolymer 1 in Example 1.

Embodiment 3 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-4 was used instead of the copolymer 1 in Example 1.

Embodiment 4. FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-5 was used instead of the copolymer 1 in Example 1.

Embodiment 5 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-6 was used instead of the copolymer 1 in Example 1.

Embodiment 6 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-9 was used instead of the copolymer 1 in Example 1.

Embodiment 7 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-10 was used instead of the copolymer 1 in Example 1.

Embodiment 8 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-14 was used instead of the copolymer 1 in Example 1.

Embodiment 9 FIG.
An organic solar cell was manufactured in the same manner as in Example 1, except that the copolymer prepared in Production Example 2-19 was used instead of the copolymer 1 in Example 1.

The photoelectric conversion characteristics of the organic solar cells manufactured in Examples 1 to 9 were measured under the conditions of 100 mW / cm ² (AM1.5), and the results are shown in Table 2 below.

In Table 2, V _oc denotes open-circuit voltage, J _sc denotes short-circuit current, FF denotes filling factor, and η denotes energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell is preferably increased. The filling factor is a value obtained by dividing the width of a rectangle drawn inside the curve by the product of the short-circuit current and the open-circuit voltage. When these three values are divided by the intensity of the irradiated light, the energy conversion efficiency is obtained, and a higher value is more preferable.

DESCRIPTION OF SYMBOLS 101 Substrate 102 1st electrode 103 Hole transport layer 104 Photoactive layer 105 2nd electrode

Claims (15)

A repeating unit derived from a compound represented by the following chemical formula 1;
A copolymer comprising a first conjugated monomer; and a second conjugated monomer different from the first conjugated monomer:

In the above chemical formula 1,
m1 and m2 are the same or different and are each independently an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other;
q1 and q2 are the same or different and are each independently an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other;
A1 and A1 ′ are the same or different and are each independently a halogen group; a substituted or unsubstituted boron group; or —SnR _a R _b R _c ;
X1, X2 and Z1 to Z5 are the same or different from each other, and each independently is S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR ′;
R _a , R _b , R _c , R, R ′, R 1 to R 4 and R 11 to R 18 are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; Group; ester group; imide group; amide group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group; A substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted ant A substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.   The first conjugated monomer and the second conjugated monomer are each independently a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted divalent heterocyclic group. 2. The copolymer according to claim 1, which comprises a combination of one or more groups. 3. The copolymer according to claim 1, wherein the first conjugate monomer and the second conjugate monomer independently include one or a combination of two or more of the following structures. 4. :

In the above structure,
a, a ', b and b' are each an integer of 1 to 5,
When a, a ', b and b' are each 2 or more, the substituents in parentheses are the same or different from each other;
X11~X30 and X33~X40, equal to or different from each other, each _{independently, S, O, Se, Te} , NR d, CR d R e, a SiR _d R e, PR _d or _GeR d _{R e,,}
X31 and X32 are the same or different from each other, and each is independently C, Si, or Ge;
R101~R124, _{R d} and _{R e,} equal to or different from each other, each independently, hydrogen, deuterium, a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; amide group; substituted Or a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, or a substituted or unsubstituted arylthioxy A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; An amine group; a substituted or unsubstituted arylphosphine group; Ku is unsubstituted phosphine oxide group; or a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted aryl group.   The copolymer according to any one of claims 1 to 3, wherein R1 to R4 and R11 to R18 are the same or different and are each independently a hydrogen; a halogen group; or a substituted or unsubstituted alkoxy group. Coalescing.   The copolymer according to any one of claims 1 to 4, wherein X1, X2 and Z1 to Z5 are each S. The copolymer according to any one of claims 1 to 5, wherein the copolymer includes a unit represented by the following chemical formula 1-1.

In the chemical formula 1-1,
m1, m2, m1 ′ and m2 ′ are the same or different from each other and are each independently an integer of 0 to 5,
When m1, m2, m1 ′ and m2 ′ are each 2 or more, the structures in parentheses are the same or different from each other;
q1, q2, q1 ′ and q2 ′ are the same or different from each other and are each independently an integer of 1 to 5,
When q1, q2, q1 ′ and q2 ′ are each 2 or more, the structures in parentheses are the same or different from each other;
X1, X2, X1 ′, X2 ′, Z1 to Z5 and Z1 ′ to Z5 ′ are the same or different from each other, and each independently represents S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR. '
E1 is a first conjugated monomer,
E2 is a second conjugated monomer,
R, R ', R1 to R4, R1' to R4 ', R11 to R18 and R11' to R18 'are the same or different and are each independently hydrogen; deuterium; halogen; nitrile; nitro; An amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted group. A substituted or unsubstituted amine group; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group. ,
f is a mole fraction and is a real number satisfying 0 <f <1;
g is a molar fraction and is a real number satisfying 0 <g <1;
f + g = 1,
n is the number of repeating units, and is an integer of 1 to 10,000. The copolymer according to claim 6, wherein the copolymer includes a unit represented by the following chemical formula 1-2.

In the above chemical formula 1-2,
f, g, n, m1, m2, m1 ′, m2 ′, q1, q2, q1 ′, q2 ′, X1, X2, X1 ′, X2 ′, Z1 to Z5, Z1 ′ to Z5 ′, E1, E2, R1, R4, R1 ′, R4 ′, R11 to R18 and R11 ′ to R18 ′ are the same as defined in Chemical formula 1-1,
R51, R51 ', R52 and R52' are the same or different and are each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. The copolymer according to any one of claims 1 to 7, wherein the copolymer includes any one of the following structures:

In the above structure,
f is a mole fraction and is a real number satisfying 0 <f <1;
g is a molar fraction and is a real number satisfying 0 <g <1;
f + g = 1,
n is the number of repeating units, and is an integer of 1 to 10,000. A first compound represented by the following chemical formula 1:
A second compound represented by the following chemical formula 2: and a method for producing a copolymer comprising a step of reacting a third compound represented by the following chemical formula 3:

In the chemical formulas 1 to 3,
m1 and m2 are the same or different and are each independently an integer of 0 to 5,
When m1 and m2 are each 2 or more, the structures in parentheses are the same or different from each other;
q1 and q2 are the same or different and are each independently an integer of 1 to 5,
When q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other;
A1, A1 ′, A2, A2 ′, A3 and A3 ′ are the same or different and are each independently a halogen group; a substituted or unsubstituted boron group; or —SnR _a R _b R _c ,
E1 is a first conjugated monomer,
E2 is a second conjugate monomer different from the first conjugate monomer,
X1, X2 and Z1 to Z5 are the same or different from each other, and each independently is S, O, Se, Te, NR, CRR ′, SiRR ′, PR, or GeRR ′;
R _a , R _b , R _c , R, R ′, R 1 to R 4 and R 11 to R 18 are the same or different and are each independently hydrogen; deuterium; a halogen group; a nitrile group; a nitro group; Group; ester group; imide group; amide group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted alkoxy group; substituted or unsubstituted aryloxy group; A substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; substituted or unsubstituted amine group; substituted or unsubstituted ant A substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group.   The method for producing a copolymer according to claim 9, wherein the method for producing a copolymer comprises a step of dissolving a first compound, a second compound, and a third compound in a solvent. A first electrode;
A second electrode provided to face the first electrode;
And one or more organic layers including a photoactive layer, provided between the first electrode and the second electrode;
An organic solar cell, wherein at least one of the organic layers contains the copolymer according to any one of claims 1 to 8. The organic layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously performs hole transport and hole injection,
The organic solar cell according to claim 11, wherein the hole transport layer, the hole injection layer, or the layer that simultaneously performs hole transport and hole injection includes the copolymer. The organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
The organic solar cell according to claim 11, wherein the electron injection layer, the electron transport layer, or the layer that simultaneously performs electron injection and electron transport includes the copolymer. The photoactive layer includes an electron donor and an electron acceptor,
The organic solar cell according to any one of claims 11 to 13, wherein the electron donor includes the copolymer.   The organic solar cell may include one or more organic materials selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generation layer, an electron blocking layer, an electron injection layer, and an electron transport layer. The organic solar cell according to any one of claims 11 to 14, further comprising a layer.

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